Nothing Special   »   [go: up one dir, main page]

WO1998022519A1 - Two step procedure for the production of semi-hard solid polyurethane moulded bodies - Google Patents

Two step procedure for the production of semi-hard solid polyurethane moulded bodies Download PDF

Info

Publication number
WO1998022519A1
WO1998022519A1 PCT/EP1997/006232 EP9706232W WO9822519A1 WO 1998022519 A1 WO1998022519 A1 WO 1998022519A1 EP 9706232 W EP9706232 W EP 9706232W WO 9822519 A1 WO9822519 A1 WO 9822519A1
Authority
WO
WIPO (PCT)
Prior art keywords
prepolymer
production
reaction
component
semi
Prior art date
Application number
PCT/EP1997/006232
Other languages
German (de)
French (fr)
Inventor
Erhard Michels
Klaus Pleiss
Franz Scholtis
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to DK97948909T priority Critical patent/DK0941262T3/en
Priority to JP52316398A priority patent/JP2001504155A/en
Priority to BR9713111-3A priority patent/BR9713111A/en
Priority to DE59705916T priority patent/DE59705916D1/en
Priority to US09/308,112 priority patent/US6147181A/en
Priority to AU73011/98A priority patent/AU7301198A/en
Priority to EP97948909A priority patent/EP0941262B1/en
Priority to SI9730132T priority patent/SI0941262T1/en
Publication of WO1998022519A1 publication Critical patent/WO1998022519A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/5045—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids

Definitions

  • the invention relates to a process for the production of solid, transparent to translucent polyurethane moldings which, because of their elastic and optical properties, can be used, for example, as an alternative material to rubber
  • PUR reaction masses based on polyester polyol are usually used to manufacture transparent, semi-rigid PU molded parts. They are particularly suitable in molded part production using the casting and / or injection process, since good results can be achieved with these over a wide range of temperatures in terms of material hardness and hardening time with regard to machine, filler, mold and mold closure technology, this is usually not common, but can be appropriate in individual cases
  • PUR molding compositions based on ether-polyol can be processed inexpensively into transparent / translucent molded parts in the same way as those based on ester if they have a significantly higher average molecular weight and a higher viscosity associated therewith through a first process step
  • the reaction with di- and / or or high-functionality components containing isocyanate end groups to give so-called OH prepolymers A reaction with di- and / or high-functionality carboxylic acids to give comparable lengthened ether / ester polyols has also proven to be suitable
  • the invention thus relates to a two-stage process for the production of compact, transparent PUR moldings by the polyisocyanate polydaddition process in a hardness of 40 to 90 Shore A by reacting
  • reaction product is selected as at least one high molecular weight compound having at least two reactive hydrogen atoms (b)
  • prepolymers in (A) to (G) are obtained, for example, by reacting the isocyanates with an ether polyol as described under (I) to (V) and are distinguished by terminal, reactive NCO groups
  • a reaction of the polyols described under (I) to (V) is also possible, instead of with isocvanates, with (AA) di- and / or highly functional carboxylic acids such as, for example, adipic acid, glutaric acid. Succinic acid and other representatives of this class of substances as well as their mixtures
  • short-chain reaction components such as H, O, di- and t ⁇ -functional OH compounds, OH-amines, di- and T ⁇ amine etc can also be used for the pre-reaction and have reacted with them and the properties of the following
  • the course of the first reaction stage to the polvol, as described above, does not necessarily require a catalytic acceleration in the case of the reaction of diol, etc. with dnsocyanate, but proceeds much faster after addition of amines, metal salts, etc.
  • ether-ester conversion AA
  • typical ester catalysts Sn, Ti-De ⁇ vate
  • the reaction temperatures are preferably 20 to 100 ° C (type AG), but are also possible and in a higher situation (AA ) also advantageous
  • the resulting OH number of the above reaction product is between 7 and
  • the viscosity of the starting product is increased significantly by the process in the usual temperature range from 20 to 50 ° C Since, as mentioned, low molecular weight hydroxv and amine end group-containing building blocks, even H 2 O, can also be introduced into the pre-reaction described, the reaction can also be started from a higher OH or OH-NHX group content The viscosity can be modified accordingly.
  • the Dabco portion is dissolved and the isocvanate component is subsequently added. After about 2 hours, the viscosity is determined, which remains unchanged even after 1 day and 7 days
  • the mixture AB in the ratio 100 38 is processed with a conventional low-pressure machine and poured into a mold and sealed.
  • the molded part with a material thickness of 5 mm and density of 1 100 kg / m 3 can be removed from the mold after 4 minutes, but has no transparency but is whitishly cloudy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a procedure for the production of solid, transparent to translucent, polyurethane moulded bodies which can be used, for instance, as an alternative material to rubber on account of their elastic and optical properties.

Description

Zweistufiges Verfahren zur Fertigung von halbharten massiven Polvurethan- FormkörpernTwo-stage process for the production of semi-hard, solid polyurethane moldings
Die Erfindung betnfft ein Verfahren zur Herstellung von massiven, transparenten bis transluzenten Polyurethan-Formkorpern, die aufgrund ihrer elastischen und optischen Eigenschaften z B als Alternativmaterial zu Gummi eingesetzt werden könnenThe invention relates to a process for the production of solid, transparent to translucent polyurethane moldings which, because of their elastic and optical properties, can be used, for example, as an alternative material to rubber
Zur Fertigung transparent halbharter PU-Formteile werden üblicherweise PUR- Reaktionsmassen auf Polyesterpolyolbasis eingesetzt Sie eignen sich besonders in der Formteilfertigung nach dem Gieß- und/oder Injektionsverfahren, da sich mit diesen über einen großen Svstemvaπationsbereich hinsichtlich Mateπalharte und Verfestigungszeit gute Ergebnisse erzielen lassen Ein besonderer Aufwand hinsichtlich der Maschinen-, Einfull-, Form- und Formenverschlußtechnik ist dabei in der Regel nicht üblich, kann aber in Einzelfallen angebracht seinPUR reaction masses based on polyester polyol are usually used to manufacture transparent, semi-rigid PU molded parts. They are particularly suitable in molded part production using the casting and / or injection process, since good results can be achieved with these over a wide range of temperatures in terms of material hardness and hardening time with regard to machine, filler, mold and mold closure technology, this is usually not common, but can be appropriate in individual cases
Auch der Einsatz von PUR-Reaktionsmassen auf Polyetherpolyolbasis ist bekannt wird aber oftmals nicht gewählt, da sich nur mit erhöhtem technischen Aufwand ein zufriedenstellender und kontinuierlich erzielbarer hoher Transparenzgrad verwirklichen laßt Die Fertigung nach dem RLM- Verfahren mit Reaktionsmassen, die sowohl reaktive Hvdroxy- wie Aminendgruppen aufweisen sowie die Zuhilfenahm e b esonderer F ormen- und Verschl ußapparate, wi e si e gem äß EP 0 299 1 17 AI beschrieben wurden, seien hierzu genannt Letztlich bot sich aber bei Einsatz von PUR-Formmassen auf Polyetherpolyolbasis stets nur ein kleines Verarbeitungsfenster, so daß demgegenüber PUR-Systeme auf Polyesterpolyolbasis stets bevorzugt eingesetzt wurden Dies erstaunhcherweise auch, wenn es sich um Anwendungen in exponierten Bereichen handelt, in denen eine hydrolytisch-mikrobielle Zersetzung der Ester-Komponenten nur durch Einbringung oftmals kostenintensiver Schutzadditive behindert wirdThe use of PU reaction masses based on polyether polyol is also known, but is often not chosen, since a satisfactory and continuously achievable high degree of transparency can only be achieved with increased technical effort.The production by the RLM process with reaction masses which have both reactive hydroxy and amine end groups and the aid of special molding and sealing apparatuses, as described in accordance with EP 0 299 1 17 AI, are mentioned here. Ultimately, however, there was always only a small processing window when using PUR molding compositions based on polyether polyol, so that, in contrast, PUR systems based on polyester polyol have always been preferred. This is also surprising when it comes to applications in exposed areas in which hydrolytic-microbial decomposition of the ester components is only hindered by the introduction of often costly protective additives
Es wurde nun gefunden, daß sich überraschend PUR-Formmassen auf Ether- Polyolbasis in gleicher Weise gunstig zu transparenten/transluzenten Formteilen verarbeiten lassen wie diejenigen auf Ester-Basis wenn sie durch eine erste Verfahrensstufe auf ein deutlich erhöhtes mittleres Molekulargewicht und eine damit verbundene erhöhte Viskosität gebracht wurden Als derartige Verfahrensstufe eignet sich wie hier folgend beschrieben besonders die Umsetzung mit Di- und/ oder hoherfunktionellen Isocyanat-Endgruppen-haltigen Komponenten zu sogenannten OH-Prepolymeren Auch eine Reaktion mit Di- und/oder hoherfunktionellen Carbonsauren zu vergleichbar verlängerten Ether-/Ester-Polyolen erweist sich als geeignetIt has now been found that, surprisingly, PUR molding compositions based on ether-polyol can be processed inexpensively into transparent / translucent molded parts in the same way as those based on ester if they have a significantly higher average molecular weight and a higher viscosity associated therewith through a first process step As a process step of this type, the reaction with di- and / or or high-functionality components containing isocyanate end groups to give so-called OH prepolymers A reaction with di- and / or high-functionality carboxylic acids to give comparable lengthened ether / ester polyols has also proven to be suitable
Gegenstand der Erfindung ist somit ein zweistufiges Verfahren zur Herstellung von kompakten, transparenten PUR-Formteilen nach dem Polyisocyanat-Polvaddi- tionsverfahren in einer Harte von 40 bis 90 Shore A durch Umsetzung vonThe invention thus relates to a two-stage process for the production of compact, transparent PUR moldings by the polyisocyanate polydaddition process in a hardness of 40 to 90 Shore A by reacting
a) organischen und/oder modifizierten organischen Polyisocyanaten mita) with organic and / or modified organic polyisocyanates
b) mindestens einer hohermolekularen Verbindung mit mindestens zwei reak- tiven Wasserstoffatomen und gegebenenfallsb) at least one high molecular weight compound with at least two reactive hydrogen atoms and optionally
c) niedermolekularen Kettenverlangerungs- und/oder Vernetzungsmitteln in Gegenwart vonc) low molecular chain extenders and / or crosslinking agents in the presence of
d) Katalysatoren undd) catalysts and
e) Hilfsmitteln und Zusatzstoffen,e) auxiliaries and additives,
dadurch gekennzeichnet, daß man als mindestens eine hohermolekulare Verbindung mit mindestens zwei reaktiven Wasserstoffatomen (b) das Reaktionsprodukt auscharacterized in that the reaction product is selected as at least one high molecular weight compound having at least two reactive hydrogen atoms (b)
(I) einem linearen EO/PO-Polyetherpolyol mit endstandigen EO-Gruppen und einem EO/PO-Verhaltms von 15 85 bis 40 60, einer OH-Zahl von 56-28 und Funktionalität von 2,0,(I) a linear EO / PO polyether polyol with terminal EO groups and an EO / PO ratio of 15 85 to 40 60, an OH number of 56-28 and functionality of 2.0,
oderor
(II) einem Gemisch eines wie unter (I) angeführten Polvetherpolyols mit einem weiteren, aber hoherfunktionellem und z B mit Glyzerin Tπmethylol- propan, Pentaerythnt oder auch Zucker gestartetem EO/PO-Polyetherpolyol (EO/PO-Verhaltms 15 85 bis 40 60) mit einer OH-Zahl von 60-25,(II) a mixture of a polyether polyol as mentioned under (I) with a further, but highly functional, EO / PO polyether polyol (EO / PO ratio 15 85 to 40 60) started, for example, with glycerol, tπmethylol propane, pentaerythne or sugar with an OH number of 60-25,
oder (III) Gemischen mehrerer linearer und verzweigter Polyetherpolyole. die jeweils wie unter (I) und (II) beschrieben, zusammengesetzt sind,or (III) Mixtures of several linear and branched polyether polyols. which are composed as described under (I) and (II),
oderor
(IV) einem Poly-THF-Ether (C4-Ether) mit mittlerem Molgewicht von 500 bis 2000(IV) a poly-THF ether (C 4 ether) with an average molecular weight of 500 to 2000
sowie auchand also
(V) Kombinationen aus (I), (II), (III) und (IV),(V) combinations of (I), (II), (III) and (IV),
umgesetzt mitimplemented with
(A) TDI (2,4-TDI zu 2,6-TDI in jedem Verhältnis) sowie daraus erhältlichen Prepolymeren,(A) TDI (2,4-TDI to 2,6-TDI in any ratio) and prepolymers obtainable therefrom,
oderor
(B) TDI-Mehrkernisocyanaten sowie den daraus erhältlichen Prepolvmeren(B) TDI multicore isocyanates and the prepolymers available therefrom
oderor
(C) MDI (4,4'-MDI, 2,4'-MDI, 2,2'-MDI m jedem Verhältnis) sowie daraus erhältlichen Prepolymeren,(C) MDI (4,4'-MDI, 2,4'-MDI, 2,2'-MDI in any ratio) and prepolymers obtainable therefrom,
oderor
(D) MDI-Mehrkernisocyanaten sowie den daraus erhältlichen Prepolymeren,(D) MDI multicore isocyanates and the prepolymers obtainable therefrom,
oderor
(E) allen weiteren, großtechnisch erhältlichen aromatischen Isocyanaten mit einer Funktionalität von mindestens 2 (NDI, p-PDI), sowie den daraus erhaltlichen Prepolymeren,(E) all other aromatic isocyanates available on an industrial scale with a functionality of at least 2 (NDI, p-PDI), and the prepolymers obtainable therefrom,
oder (F) allen weiteren großtechnisch erhältlichen ahphatischen Isocyanaten mit einer Funktionalitat von mindestens 2 (LPDI, HDI H-MDI), sowie den daraus erhältlichen Prepolymeren,or (F) all other ahphatic isocyanates available on a large industrial scale with a functionality of at least 2 (LPDI, HDI H-MDI), and the prepolymers obtainable therefrom,
oderor
(G) Isocyanatmischungen aus (A) bis (F)(G) isocyanate mixtures from (A) to (F)
Die jeweils angeführten Prepolymere in (A) bis (G) werden z B durch Umsetzung der Isocyanate mit einem wie unter (I) bis (V) beschriebenen Etherpolyol erhalten und zeichnen sich durch endstandige, reaktionsfähige NCO-Gruppen ausThe respectively mentioned prepolymers in (A) to (G) are obtained, for example, by reacting the isocyanates with an ether polyol as described under (I) to (V) and are distinguished by terminal, reactive NCO groups
Eine Umsetzung der unter (I) bis (V) beschriebenen Polyole ist ebenfalls, statt mit Isocvanaten, möglich mit (AA)Dι- und/oder hoherfunktionellen Carbonsauren wie z B Adipinsaure, Glutarsaure. Bernsteinsaure und weiteren Vertretern dieser Stoffklasse sowie auch deren GemischenA reaction of the polyols described under (I) to (V) is also possible, instead of with isocvanates, with (AA) di- and / or highly functional carboxylic acids such as, for example, adipic acid, glutaric acid. Succinic acid and other representatives of this class of substances as well as their mixtures
Ferner können noch "kurzkettige" Reaktionsbestandteile wie H-,0, di- und tπfunk- tionelle OH-Verbindungen, OH-Amine, Di- und Tπamine etc mit zur Vorreaktion eingesetzt werden und mitreagiert haben und die Eigenschaften des folgend zumFurthermore, "short-chain" reaction components such as H, O, di- and tπ-functional OH compounds, OH-amines, di- and Tπamine etc can also be used for the pre-reaction and have reacted with them and the properties of the following
Polyurethan umgesetzten Materials gezielt andernChange the polyurethane material
Der Ablauf der ersten Reaktionsstufe zum Polvol, wie oben beschrieben bedarf zwar im Fall der Reaktion von Diol etc mit Dnsocyanat nicht unbedingt einer katalytischen Beschleunigung, verlauft aber nach Zusatz von Aminen Metallsalzen etc wesentlich schnellerThe course of the first reaction stage to the polvol, as described above, does not necessarily require a catalytic acceleration in the case of the reaction of diol, etc. with dnsocyanate, but proceeds much faster after addition of amines, metal salts, etc.
Bei der Ether-Ester-Umsetzung (AA) sind typische Ester-Katalysatoren (Sn-, Ti- Deπvate) zu bevorzugen Die Reaktionstemperaturen liegen bevorzugt bei 20 bis 100°C (Typ A-G), sind aber auch hoher möglich und in Situation (AA) auch vorteilhaftIn the ether-ester conversion (AA), typical ester catalysts (Sn, Ti-Deπvate) are preferred. The reaction temperatures are preferably 20 to 100 ° C (type AG), but are also possible and in a higher situation (AA ) also advantageous
Die resultierende OH-Zahl des o a Umsetzungsproduktes liegt zwischen 7 bisThe resulting OH number of the above reaction product is between 7 and
50 mg KOH/g, bevorzugt zwischen 10 bis 28 mg KOH/g Die Viskosität des Ausgangsproduktes wird im üblichen Temperatur-Einsatzbereich von 20 bis 50°C durch das Verfahren deutlich erhöht Da auch, wie angeführt, niedermolekulare Hydroxv- und Amin-Endgruppen-haltige Bausteine, sogar H20, mit in die beschriebene Vorreaktion eingebracht werden können, kann die Reaktion auch von einem höheren OH- bzw OH- NHX-Grup- pengehalt gestartet werden Die Viskosität ist entsprechend modifiziert zu erreichen. 50 mg KOH / g, preferably between 10 to 28 mg KOH / g. The viscosity of the starting product is increased significantly by the process in the usual temperature range from 20 to 50 ° C Since, as mentioned, low molecular weight hydroxv and amine end group-containing building blocks, even H 2 O, can also be introduced into the pre-reaction described, the reaction can also be started from a higher OH or OH-NHX group content The viscosity can be modified accordingly.
BeispieleExamples
1. OH-Prepolymer-Beispiele1. OH prepolymer examples
BeispieltabelleExample table
Figure imgf000008_0001
Figure imgf000008_0001
1 1 Durchfuhrung1 1 implementation
Nach Vorlage der OH-Komponenten und Temperierung auf 50°C wird der Dabco-Anteil gelost und folgend die Isocvanatkomponente zugesetzt Nach ca 2 h wird die Viskosität bestimmt, die sich unverändert auch nach 1 d und 7 d auf gleichem Niveau befindetAfter submission of the OH components and temperature control at 50 ° C., the Dabco portion is dissolved and the isocvanate component is subsequently added. After about 2 hours, the viscosity is determined, which remains unchanged even after 1 day and 7 days
1 2 Ebenfalls möglich ist die anteilige Vorlage reaktiver OH-Komponenten so daß ein aufkonzentriertes Reaktionsgemisch vorliegt, das ebenfalls bei 50°C mit dem Dabco und der Isocyanatkomponente versetzt wird Nach Abreak- tion wird die restliche Menge der OH-reaktiven Komponente zugesetzt und man erhalt ein gleich nach dem Verfahren 1 1 hergestelltes Produkt Umsetzungsbeispiele1 2 It is also possible to provide reactive OH components in portions, so that a concentrated reaction mixture is present, which is also admixed with Dabco and the isocyanate component at 50 ° C. After the reaction, the remaining amount of the OH-reactive component is added and this is obtained a product produced according to method 1 1 Implementation examples
Das unumgesetzte Basispolyol (a) der Beispieltabelle 1 wird mit folgenden Reaktionspartnern umgesetztThe unreacted base polyol (a) from Example Table 1 is reacted with the following reactants
A-Komponente Polyol (a) 93,87A component polyol (a) 93.87
Butandιol-1 ,4 6,00Butanediol-1, 4 6.00
DBTL 0,03DBTL 0.03
Dabco (kπst ) 0,10Dabco (kπst) 0.10
B-Komponente MDI-Prepolymer aus 4,4'-MDI Desmodur CD und Etherpolyol (a) mit einem NCO-Gehalt von 20 %B-component MDI prepolymer from 4,4'-MDI Desmodur CD and ether polyol (a) with an NCO content of 20%
Materialtemperaturen je 35°CMaterial temperatures of 35 ° C each
Die Mischung A B im Verhältnis 100 38 wird mit einer üblichen Nieder- druckmaschine verarbeitet und in eine Form gegossen und verschlossen Das Formteil mit einer Materialstarke von 5 mm und Dichte von 1 100 kg/m3 kann nach 4 Min entformt werden, weist aber keine Transparenz auf, sondern ist weißlich trübThe mixture AB in the ratio 100 38 is processed with a conventional low-pressure machine and poured into a mold and sealed. The molded part with a material thickness of 5 mm and density of 1 100 kg / m 3 can be removed from the mold after 4 minutes, but has no transparency but is whitishly cloudy
Das Umsetzungsprodukt aus Beispiel 1 1 wird in vorheriger Rezeptur eingesetzt Bei gleicher Vorgehensweise und Berücksichtigung der geringeren OH-Zahl des jetzt eingesetzten OH-Prepolymeren (A B = 100 36) laßt sich nach 4 Min ein transparentes Formteil entformenThe reaction product from Example 11 is used in a previous recipe. With the same procedure and taking into account the lower OH number of the OH prepolymer now used (A B = 100 36), a transparent molded part can be removed from the mold after 4 minutes
Als Rezepturvariante für den Direktansohlungsprozeß wird folgende Variante gewähltThe following variant is selected as the recipe variant for the direct soling process
A-Komponente Polyol (a) 92,97A component polyol (a) 92.97
Butandιol-1,4 6,00Butanediol-1.4 6.00
Ethandiol 0,50Ethanediol 0.50
DBTL 0,03DBTL 0.03
Dabco (kπst ) 1,00Dabco (kπst) 1.00
B-Komponente (s Beispiel 2 1)B component (see example 2 1)
Mateπ altemperaturen je 35°C Das durch Schneckenvermischung nach dem Desma- Verfahren bereitete Reaktionsgemisch (A B = 100 41 ) wird in eine auf ca 50°C temperierte Form eingetragen und die Form nach dem Desma- Verfahren verschlossenMateπ temperatures each 35 ° C The reaction mixture (AB = 100 41) prepared by screw mixing according to the Desma process is introduced into a mold at a temperature of about 50 ° C. and the mold is sealed using the Desma process
Nach ca 2,5 Min wird die Form geöffnet und man erhalt ein trub-weißes Formteil, an das im Folgeschritt ein weiteres PUR-Mateπal angespntzt werden konnteAfter approx. 2.5 minutes, the mold is opened and a cloudy-white molded part is obtained, to which a further PUR material could be spun in the subsequent step
Wie unter 2 3 beschrieben, bei Austausch des Polvols (a) gegen das Polyol (1 1), laßt sich beim nachgeregelten Mischungsverhältnis (A B = 100 39) nach 2,5 Min jetzt aber ein transparentes Formteil entformen, an das eben- falls im Folgeschritt ein weiteres PUR-Mateπal angespritzt werden kann As described under 2 3, when replacing the polvol (a) with the polyol (1 1), a transparent molded part can now be removed from the mold after 2.5 minutes with the readjusted mixing ratio (AB = 100 39) Subsequent step, another PUR material can be injected

Claims

Patentansprücheclaims
1 Zweistufiges Verfahren zur Fertigung von halbharten massiven Polyurethan-Formkorpern, die eine hohe Transparenz auch bei unterschiedlicher Formteildicke aufweisen, durch Umsetzung von1 Two-stage process for the production of semi-hard, solid polyurethane moldings, which are highly transparent even with different molded part thicknesses, by implementing
a) organischen und/oder modifizierten organischen (Poly)ιsocvanaten
Figure imgf000011_0001
a) organic and / or modified organic (poly) isocvanates
Figure imgf000011_0001
b) einem Etherpolyol, wie unter (I)-(V) beschrieben das in einer ersten Stufe mit OH-reaktiven Reaktionspartnern wie aromatischen und aliphatischen Isocvanatdeπvaten zu einem OH-Endgruppen-haltigen OH-Prepolymer umgesetzt wird, mitb) an ether polyol, as described under (I) - (V), which is reacted in a first stage with OH-reactive reactants such as aromatic and aliphatic isocyanate derivatives to form an OH prepolymer-containing OH prepolymer
c) niedermolekularen Kettenverlangerungs- und/oder Vernetzungsmitteln in Gegenwart vonc) low molecular chain extenders and / or crosslinking agents in the presence of
d) Amin- und/oder Metallsalzkatalysatoren undd) amine and / or metal salt catalysts and
e) Hilfsmitteln und Zusatzstoffen,e) auxiliaries and additives,
dadurch gekennzeichnet, daß das OH-Prepolvmer (b) eine OH-Zahl von 7 bis 56 mg KOH g aufweist und keine reaktionsfähigen NCO-Gruppen mehr enthaltcharacterized in that the OH prepolymer (b) has an OH number of 7 to 56 mg KOH g and no longer contains reactive NCO groups
2 Verfahren gemäß Anspruch 1, dadurch gekennzeichnet daß die Komponente b) anteilig kurzkettige Reaktionsbestandteile wie H-,0, di- und tπ- funktionelle OH- Verbindungen, OH-Amine, Di- und Tπamine enthalt die auch mit zur Reaktion zum OH-Prepolymer gebracht werden2 The method according to claim 1, characterized in that component b) contains short-chain reaction components such as H-, 0-, di- and tπ- functional OH compounds, OH amines, di- and Tπamine also with the reaction to the OH prepolymer to be brought
3 Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Komponente b) unter Zuhilfenahme von Amin- und/oder Metallsalzkatalvsatoren hergestellt wird3 Process according to claim 1, characterized in that component b) is produced with the aid of amine and / or metal salt catalysts
4 Verfahren gemäß Anspruch 1 , dadurch gekennzeichnet, daß die Komponente b) das Reaktionsprodukt aus einem Etherpolvol und einer Di- und/ oder hoherfunktionellen Carbonsaure ist, die keine freien reaktionsfähigen Carbonsauregruppen mehr enthalt4 The method according to claim 1, characterized in that component b) the reaction product of an ether polvol and a di- and / or a highly functional carboxylic acid that no longer contains free reactive carboxylic acid groups
Verfahren gemäß Anspruch 1 zur Fertigung von Schuhsohl en,Method according to claim 1 for the production of shoe soles,
Schuhsohlenbauteilen, technischen Dichtungen und mechanisch belasteten Rollkorpern Shoe sole components, technical seals and mechanically loaded roller bodies
PCT/EP1997/006232 1996-11-20 1997-11-10 Two step procedure for the production of semi-hard solid polyurethane moulded bodies WO1998022519A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DK97948909T DK0941262T3 (en) 1996-11-20 1997-11-10 Two-step process for making semi-hard solid polyurethane molds
JP52316398A JP2001504155A (en) 1996-11-20 1997-11-10 Two-step method for producing semi-rigid, solid polyurethane molded articles
BR9713111-3A BR9713111A (en) 1996-11-20 1997-11-10 Two-step process for the production of molded semi-rigid polyurethane items.
DE59705916T DE59705916D1 (en) 1996-11-20 1997-11-10 TWO-STAGE PROCESS FOR PRODUCING SEMI-HARD SOLID POLYURETHANE MOLDED BODIES
US09/308,112 US6147181A (en) 1996-11-20 1997-11-10 Two step procedure for the production of semi-hard solid polyurethane molded bodies
AU73011/98A AU7301198A (en) 1996-11-20 1997-11-10 Two step procedure for the production of sem-hard solid polyurethane moulde d bodies
EP97948909A EP0941262B1 (en) 1996-11-20 1997-11-10 Two step procedure for the production of semi-hard solid polyurethane moulded bodies
SI9730132T SI0941262T1 (en) 1996-11-20 1997-11-10 Two step procedure for the production of semi-hard solid polyurethane moulded bodies

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19648012.4 1996-11-20
DE19648012A DE19648012A1 (en) 1996-11-20 1996-11-20 Two-stage process for the production of semi-hard solid polyurethane moldings

Publications (1)

Publication Number Publication Date
WO1998022519A1 true WO1998022519A1 (en) 1998-05-28

Family

ID=7812236

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/006232 WO1998022519A1 (en) 1996-11-20 1997-11-10 Two step procedure for the production of semi-hard solid polyurethane moulded bodies

Country Status (11)

Country Link
US (1) US6147181A (en)
EP (1) EP0941262B1 (en)
JP (1) JP2001504155A (en)
AU (1) AU7301198A (en)
BR (1) BR9713111A (en)
DE (2) DE19648012A1 (en)
DK (1) DK0941262T3 (en)
ES (1) ES2170422T3 (en)
PT (1) PT941262E (en)
TW (1) TW412547B (en)
WO (1) WO1998022519A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451049B2 (en) 1998-04-29 2002-09-17 Sorin Biomedica Cardio, S.P.A. Stents for angioplasty

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030006526A1 (en) * 2001-04-30 2003-01-09 Fusion Specialties, Inc. Molded Display Forms
US20060074147A1 (en) * 2004-10-06 2006-04-06 Mayo Michael A Cast material having color effect
DE102005059710A1 (en) * 2005-12-12 2007-06-14 Basf Ag Prepolymers and cellular polyisocyanate polyaddition products prepared therefrom
DE102006042338A1 (en) * 2006-09-08 2008-03-27 Evonik Goldschmidt Gmbh Use of urethane or urea groups containing polyethers for the stabilization of polyurethane foams
US8496860B2 (en) * 2009-07-31 2013-07-30 Fusion Specialties, Inc. Foam-backed, hollow articles made by cold rotational molding

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2649739A1 (en) * 1976-10-29 1978-05-03 Ihara Chemical Ind Co Transparent polyurethane elastomers prepn. - from poly:isocyanate, aromatic di:amine, poly:ol and poly:ol or aminoalcohol with urethane bond
US4107151A (en) * 1976-10-28 1978-08-15 Ihara Chemical Company Co., Ltd. Process for producing urethane elastomer
US4306052A (en) * 1980-09-25 1981-12-15 The Upjohn Company Thermoplastic polyester polyurethanes
US4521582A (en) * 1983-08-18 1985-06-04 Bayer Aktiengesellschaft Thermoplastic polyurethanes having a high heat stability, based on naphthylene diisocyanate, their production and their use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3899623A (en) * 1972-04-10 1975-08-12 Toray Industries Synthetic leather combination of needle-punched fabric and polyetherester polyurethane
IT1198176B (en) * 1986-11-27 1988-12-21 New Flex Srl PROCEDURE AND EQUIPMENT FOR THE MOLDING OF POLYURETHANE ITEMS

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4107151A (en) * 1976-10-28 1978-08-15 Ihara Chemical Company Co., Ltd. Process for producing urethane elastomer
DE2649739A1 (en) * 1976-10-29 1978-05-03 Ihara Chemical Ind Co Transparent polyurethane elastomers prepn. - from poly:isocyanate, aromatic di:amine, poly:ol and poly:ol or aminoalcohol with urethane bond
US4306052A (en) * 1980-09-25 1981-12-15 The Upjohn Company Thermoplastic polyester polyurethanes
US4521582A (en) * 1983-08-18 1985-06-04 Bayer Aktiengesellschaft Thermoplastic polyurethanes having a high heat stability, based on naphthylene diisocyanate, their production and their use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273494B2 (en) 1997-04-29 2007-09-25 Sorin Biomedica Cardio S.R.L. Stents for angioplasty
US6451049B2 (en) 1998-04-29 2002-09-17 Sorin Biomedica Cardio, S.P.A. Stents for angioplasty

Also Published As

Publication number Publication date
DK0941262T3 (en) 2002-04-08
EP0941262B1 (en) 2001-12-19
AU7301198A (en) 1998-06-10
US6147181A (en) 2000-11-14
JP2001504155A (en) 2001-03-27
BR9713111A (en) 2000-04-11
ES2170422T3 (en) 2002-08-01
DE19648012A1 (en) 1998-05-28
PT941262E (en) 2002-06-28
DE59705916D1 (en) 2002-01-31
TW412547B (en) 2000-11-21
EP0941262A1 (en) 1999-09-15

Similar Documents

Publication Publication Date Title
EP1797129B1 (en) Method for producing flexible polyurethane foams
DE69417827T2 (en) Bis (N-alkylaminocyclohexyl) methane as a curing agent for polyurethanes and polyureas
DE19618392A1 (en) Process for the production of elastic polyurethane moldings with a compact surface and cellular core
DE2040644A1 (en) New aromatic diamines, a process for their production and their use for the production of polyurethanes
DE3718935A1 (en) STORAGE POLYOL MIXTURES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF MOLDED POLYURETHANE BODIES
DE2843739C3 (en) Process for the production of substantially homogeneous polyurethane elastomers
DE69104197T2 (en) MICROCELLULAR POLYURETHANE POLYMERS MADE FROM ISOCYANATE-TERMINATED POLYOXYTETRAMETHYLENE GLYCOLES.
EP1024156B1 (en) Polyurethane casting elastomers based on durol diisocyanate
DE69027570T2 (en) Process for producing flexible flexible polyurethane foam
DE1694136A1 (en) Process for the production of polyurethanes
EP0024555A1 (en) Process for the production of diisocyanato toluene mixtures contaning an increased amount of 2,6-diisocyanato toluene and production of polyurethane elastomers using these mixtures
EP0941262B1 (en) Two step procedure for the production of semi-hard solid polyurethane moulded bodies
EP2643377B1 (en) Molded polyurethane elastomer parts made of diphenylmethane diisocyanate-based nco prepolymers and metal salt complexes, and a method for producing same
DE10319242A1 (en) Starting compounds for the production of polyurethanes
DE3138422A1 (en) METHOD FOR PRODUCING CELLED POLYURETHANE ELASTOMERS BASED ON 4,4'-DIISOCYANATO-DIPHENYLETHANE-1,2
DE1243865B (en) Polyisocyanate mixtures for the production of plastics
EP0148462B1 (en) Process for the in-situ preparation of urea groups containing diisocyanates in polyols, dispersions and solutions prepared according to this process and their use
DD282699A5 (en) PROCESS FOR PREPARING POLYURETHANE-UREA ELASTOMERS
DE2207142A1 (en) Polyurethanes and a process for their preparation
EP0356862A2 (en) Polyurethane-based cellular mouldings, their manufacture and use as shoe soles
DE2857586C2 (en) Storage-stable, activated NCO pre-adduct mixtures
DE1570599C3 (en) Process for the production of high molecular weight elastic polyurethanes with shaping. An9: Bayer AG, 5090 Leverkusen
DE2649739C2 (en) Process for the manufacture of urethane elastomers
DE2713776C2 (en)
DE1769869C3 (en) Process for the production of high molecular weight crosslinked polyurethanes

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT LU MC

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997948909

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09308112

Country of ref document: US

ENP Entry into the national phase

Ref country code: JP

Ref document number: 1998 523163

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/004665

Country of ref document: MX

WWP Wipo information: published in national office

Ref document number: 1997948909

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWG Wipo information: grant in national office

Ref document number: 1997948909

Country of ref document: EP